A. Field of the Invention
The present invention relates to a single-part, single-phase, liquid color developer concentrate for use in color photographic development and a method for processing image-wise exposed photographic color silver halide emulsions using the color developer concentrate.
B. Description of the Related Art
Exposed photographic color silver halide emulsions are generally processed through the steps of color development, desilvering, washing and stabilization, usually using the following processing solutions: color developer, bleaching solution, fixer (or a combined bleach-fixing solution), wash water and/or stabilizing solution. These processing solutions are available as diluted, single-part, ready-to-use solutions, or are prepared either from solid chemicals or sets of multiple liquid concentrates, which must be mixed and diluted prior to use.
For the developer processing step, sets of multiple liquid concentrates have been used to prepare the color developer replenisher and working strength developer. These sets of multiple liquid concentrates have been required in order to separate individual components necessary to form the color developer composition to avoid unwanted chemical reactions between these components, wherein the chemical reactions cause deterioration of the developer concentrate during long term storage. The sets of multiple liquid concentrates have found wide-reaching commercial success within the photographic processing industry. However, mixing and diluting multiple concentrates to form a single developer processing solution requires a specific addition order of the concentrates and dilution water. Improper addition order may cause severe precipitation of the active ingredients, compromising the performance of the solution and causing mechanical malfunction of the processor.
Therefore, there is a need in the color photographic processing industry to combine the multiple liquid concentrates into a single-part concentrate in order to simplify the preparation of working solutions and replenisher solutions, minimize the chance of mixing error, and reduce packaging waste. At the same time, the long-term stability of the liquid concentrate compositions must be maintained.
For color photographic processing, one or more p-phenylenediamine or a derivative or salt thereof (hereinafter xe2x80x9cp-phenylenediaminexe2x80x9d) is required in the color developing composition to function as a color developing agent. To stabilize the p-phenylenediamine, preservatives of hydroxylamine or a derivative thereof (hereinafter xe2x80x9chydroxylaminexe2x80x9d) are required. However, p-phenylenediamine and hydroxylamine react in liquid form in aqueous solutions. Further, p-phenylenediamine is not very soluble at the high pH levels required for color photographic processing. Thus, incorporation of these chemicals into a single aqueous solution that is stable and simple to manufacture has not heretofore been possible.
It is recognized that these disadvantageous chemical reactions are unique to the color photographic processing industry. Black and white photographic processing single-part concentrate solutions are known, such as, for example, U.S. Pat. No. 5,376,510 to Parker et al. and U.S. Pat. No. 4,987,060 to Marchesano, as well as many commercially available products and compositions. However, since color developing compositions are different from black and white developing compositions, there is still a need in the industry to produce a single-part liquid color developer concentrate useful in forming color developer replenishers and color working strength developers. Thus, numerous investigations have been made in the industry directed toward developing single-part color developer concentrates.
Papai (U.S. Pat. No. 5,891,609) teaches a heterogeneous, single-part color developer concentrate having distinct layers or phases: an aqueous lower phase, an upper phase containing p-phenylenediamine developing agent dissolved in an organic solvent of single ring heterocyclic amide, and an optional middle phase consisting of solid particles suspended between the other two layers. Such a heterogeneous product is disadvantageous because use of only a portion of the contents of the container can result in an uneven dosage of the active ingredients, thus affecting the consistency of the developer performance. Additionally, residue remaining in the developer concentrate container upon dispensing and mixing the product can result in an uneven dosage of the active ingredients. Thus, a single-phase developer concentrate is desirable.
Tappe et al (U.S. Pat. No. 6,251,573) teach a single-part color developer concentrate which comprises at least two phases. While being free of any residue or precipitation, it still retains the disadvantages of being non-homogeneous with the concomitant lack of uniformity when using only a portion of the concentrate when dosing for replenishment.
Kim et al (U.S. Pat. No. 5,914,221) teach a single-part color photographic processing composition in slurry form, with a water content of less than 50% (w/w). While providing a substantial advantage in product uniformity and high compactness, further conveniences in use and manufacturing simplification are desirable.
Hashimoto et al (EP 800111) teaches a low viscosity, pourable, slurry-form, single-part color photographic developer containing 0.1 to 10% of a water soluble polymer and 50 to 250% water based on the weight of the solid ingredients. It is taught that the slurry is easily transferred and readily dispersible. However, the slurry requires high quantities of alkali compounds in order to solubilize the p-phenylenediamine developing agent in the high water content medium and to make a developer replenisher having a pH 12.0 or greater on dilution and dissolution.
Darmon et al (U.S. Pat. Nos. 6,017,687 and 6,077,651) teaches the use of a p-phenylenediamine developing agent in free-base form. The developing agent is dissolved in an organic solvent dominated medium to form a highly compact, single-part, single-phase, liquid developer concentrate having a weight ratio of water to organic solvent of 15:85 to 50:50. However, to obtain the single-phase, liquid developer concentrate, additional manufacturing steps of in-process filtration and washing are necessary for elimination of inorganic salts formed during the dissolution of the developing agent. These inorganic salts have a low solubility in the organic solvent and thus form a precipitate which must be removed during manufacture of the developer concentrate. In addition, the high level of organic solvent in the developer concentrate may have a deleterious effect on the sensitometric performance of some color photographic emulsions, resulting in undesirable image quality. Further, the high level of organic solvents in the concentrate creates an undesirable environmental impact.
Darmon et al (U.S. Pat. No. 6,228,567) requires the use of the p-phenylenediamine color developing agent in free base form only, including the additional manufacturing steps of precipitating and washing to remove inorganic salts form the commercially available salts of color developing agents.
As seen from the review of the state of the art, use of high levels of organic solvent enables dissolution of p-phenylenediamine, but hinders dissolution of various salts necessary or desirable for use in a developer concentrate. Further, high levels of organic solvent can have a deleterious effect on the sensitometric performance of some color photographic emulsions, resulting in undesirable image quality. Again, the additional manufacturing steps of precipitation and washing to remove inorganic salts from the commercially available salts of color developing agents contribute to the difficulty in producing a single-part, single-phase color developer concentrate.
Thus, there is a continuing need in the industry to provide a homogeneous single-part color developer concentrate that is stable, simple to dilute and mix, easy to manufacture, does not compromise photographic performance, and which has minimal environmental impact, such as being used at lower replenishment rates, thereby reducing the discharge of waste to the environment and providing reduced chemical and biological oxygen demand.
The present invention provides a single-part, single-phase, liquid color developer concentrate for processing silver halide color photographic materials.
In another aspect, the present invention provides a single-part, single-phase, liquid color developer concentrate comprising:
a) a color developing agent comprising p-phenylenediamine or a derivative or a salt thereof;
b) an aqueous solution comprising water and at least one organic solvent of Formula (I) as follows: 
wherein X is selected from the group consisting of xe2x80x94OR1, H and methyl; R1 is selected from the group consisting of H, acyl, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R2 and R4 can be the same or different and are independently selected from the group consisting of H, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R3 is selected from the group consisting of H, alkoxyl of 1 to 2 carbons, alkyl of 1 to 2 carbons, aryl, arylalkoxyl, aryloxycarbonyl and substituted or unsubstituted alkoxycarbonyl; n is an integer from 1 to 12; and m is 0 or 1,
wherein the organic solvent of Formula (I) is present in the aqueous solution in an amount such that the weight ratio of water to said organic solvent is from about 60:40 to about 95:5 and wherein dissolved alkaline components and inorganic and organic alkaline salts are present in amounts such that a molar ratio of [Na+]/[K+] is at least about 1:2 or greater in the color developer concentrate.
Preferably, the color developer concentrate further comprises dissolved alkaline components and inorganic and organic alkaline salts, preferably sodium salts, such that a molar ratio of total [Na+]/[K+] is in the range of from about 1:1 to about 3:2, and more preferably at least about 2:1, in the liquid color developer concentrate.
In another embodiment, the present invention provides a single-part, single-phase, liquid color developer concentrate comprising:
a) a color developing agent comprising p-phenylenediamine or a derivative or a salt thereof;
b) an aqueous solution comprising water and at least one organic solvent of Formula (I) as follows: 
wherein X is selected from the group consisting of xe2x80x94OR1, H and methyl; R1 is selected from the group consisting of H, acyl, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R2 and R4 can be the same or different and are independently selected from the group consisting of H, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R3 is selected from the group consisting of H, alkoxyl of 1 to 2 carbons, alkyl of 1 to 2 carbons, aryl, arylalkoxyl, aryloxycarbonyl and substituted or unsubstituted alkoxycarbonyl; n is an integer from 1 to 12; and m is 0 or 1,
wherein a weight ratio of water to said organic solvent of Formula (I) is from about 60:40 to about 95:5, a molar ratio of the organic solvent of Formula (I) to a free base of the p-phenylenediamine or p-phenylenediamine derivative is from about 3:1 to about 30:1, and wherein dissolved alkaline components and inorganic and organic alkaline salts are present in amounts such that a molar ratio of [Na+]/[K+] is at least about 1:2 or greater in the color developer concentrate.
In another aspect, the present invention provides a method for processing image-wise exposed photographic color silver halide emulsions, comprising the steps of:
mixing the homogeneous single-part, single-phase, liquid color developer concentrate in water so as to form a processing solution; and
processing the exposed photosensitive material with said processing solution.
The single-part, single-phase, liquid color developer concentrate of the invention is a single-phase, liquid chemical composition that is simple to manufacture and has the advantages of being easy to dilute, having reduced packaging waste, having less effluent volume due to the low replenishment rate, having minimal effect on the sensitometric performance of color photographic emulsions, and having minimal environmental impact. Further, the single-part, single-phase liquid color developer concentrate of the invention offers the flexibility of using either the full content of the package of developer concentrate or only part of the package of developer concentrate to form a developer replenisher or working strength developer due to the single-phase, homogeneous nature of the developer concentrate. Other features of the present invention include effective and rapid dissolution, compactness, ease of handling and higher user productivity. Further advantages will be apparent to practitioners in the art upon review of the following detailed description.
The single-part, single-phase, liquid color developer concentrate according to the present invention is prepared by combining p-phenylenediamine or a derivative or salt thereof, preferably a salt, and hydroxylamine or a derivative thereof with other photographic processing components in an aqueous solution comprising water and at least one organic solvent of Formula (I), wherein the water: organic solvent ratio is at least about 60:40 by weight and the molar ratio of [Na+]/[K+] is at least about 1:2 or greater. Preferably, a molar ratio of the organic solvent of Formula (I) to a free base of the p-phenylenediamine or p-phenylenediamine derivative is from about 3:1 to about 30:1. The molar ratio of the organic solvent of Formula (I) to p-phenylenediamine or a derivative or salt thereof is based on the molar quantity of the free base p-phenylenediamine as known to a practitioner in the art. However, p-phenylenediamine as used in the color developer concentrate of the invention described herein may be in the form of a p-phenylenediamine free base, a p-phenylenediamine derivative or a p-phenylenediamine salt.
Preferably, the color developer concentrate comprises:
a) a color developing agent comprising p-phenylenediamine or a derivative or a salt thereof; and
b) an aqueous solution comprising water and at least one organic solvent of Formula (I) in a weight ratio of at least about 60:40, wherein Formula (I) is as follows: 
wherein X is selected from the group consisting of xe2x80x94OR1, H and methyl; R1 is selected from the group consisting of H, acyl, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R2 and R4 can be the same or different and are independently selected from the group consisting of H, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R3 is selected from the group consisting of H, alkoxyl of 1 to 2 carbons, alkyl of 1 to 2 carbons, aryl, arylalkoxyl, aryloxycarbonyl and substituted or unsubstituted alkoxycarbonyl; n is an integer from 1 to 12; and m is 0 or 1,
wherein a weight ratio of water to said organic solvent of Formula (I) is from about 60:40 to about 95:5, a molar ratio of the organic solvent of Formula (I) to a free base of the p-phenylenediamine or p-phenylenediamine derivative is from about 3:1 to about 30:1, and/or wherein dissolved alkaline components and inorganic and organic alkaline salts are in an amount such that the molar ratio of [Na+]/[K+] is at least about 1:2 or greater in the color developer concentrate.
P-phenylenediamine or a derivative or salt thereof is present in a concentration of about 10.0 to 40.0 mM, preferably in a concentration of 18.0 to 30.0 mM, in a developer replenisher formed by diluting the color developer concentrate in water by a volume factor of about 2 to about 17, preferably about 2 to about 10. Preferably, p-phenylenediamine or a derivative or salt thereof is present in an amount such that a molar ratio of the organic solvent of Formula (I) to a free base of the p-phenylenediamine, or p-phenylenediamine derivative is from about 3:1 to about 30:1.
It is preferred to use a salt of p-phenylenediamine because salts of p-phenylenediamine are commercially available and offer greater safety in handling, including lower toxicity. Further, when a salt of p-phenylenediamine is used, the need for in-process filtration and washing steps is eliminated. This eases manufacturing by removing the need for additional equipment and lowering the production cost to prepare the color developer concentrate.
Suitable derivatives and salts of p-phenylenediamine include, but are not limited to, for example:
4-amino-3-methyl-N-ethyl-N((beta)-(methanesulfonamido)ethyl) aniline,
N,N-diethyl-p-phenylenediamine,
2-amino-5-diethylamino-toluene,
4-amino-N-ethyl-N-(xcex1-methanesulphonamidoethyl)-m-toluidine,
4-amino-3-methyl-N-ethyl-N-(xcex1-hydroxy-ethyl)-aniline,
4-amino-3-(xcex1-methylsulfonamidoethyl)-N,N-diethylaniline,
4-amino-N,N-diethyl-3-(Nxe2x80x2-methyl-xcex1-methylsulfonamido)-aniline,
N-ethyl-N-methoxy-ethyl-3-methyl-p-phenylenediamine,
4-amino-3-methyl-N,N-diethylaniline,
4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline,
4-amino-N-ethyl-N-(2-hydroxyethyl)aniline,
4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline,
4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline,
N-(2-amino-5-N, N-diethylaminophenylethyl)methanesulfonamide,
N,N-dimethyl-p-phenylenediamine,
4-amino-3-methyl-N-ethyl-N-(2-methoxyethyl)aniline,
4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline,
4-amino-3-methyl-N-ethyl-N-(2-butoxyethyl)aniline,
and the like, and salts thereof. A preferred salt is 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylene diamine sesquisulfate. Other suitable salts and derivatives of p-phenylenediamine are known to practitioners in the art.
Hydroxylamines and derivatives or salts thereof for use in the color developer concentrate as a preservative and/or antioxidant are of the following general Formula (IV): 
wherein R5 and R6 each are independently selected from a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heteroaromatic group, with the proviso that both R5 and R6 cannot be hydrogen atoms at the same time. Alternately, R5 and R6, taken together, may form a heterocyclic ring with the nitrogen atom. The heterocyclic structure is typically a 5- or 6-membered ring constructed of carbon, hydrogen, halogen, oxygen, nitrogen and/or sulfur atoms, and may be either saturated or unsaturated. Most often, R5 and R6 are independently selected from alkyl or alkenyl groups preferably having 1 to 10 carbon atoms, most preferably 1 to 5 carbon atoms. The nitrogenous heterocyclic rings formed by R5 and R6 taken together include, but are not limited to, piperidyl, pyrrolidinyl, N-alkylpiperazyl, morpholyl, indolinyl, and benzotriazole groups, for example. Illustrative, non-limiting examples of the compounds of Formula (IV) are given below.
The compounds of Formula (IV) may be used alone or in an admixture of two or more. The compounds of Formula (IV) are preferably added to the working strength developer and developer replenisher in an amount of about 5 to 150 mM, more preferably in an amount of about 10 to 100 mM. The addition of alkanolamines such as hydroxylamine-N,Nxe2x80x2-diethanesulfonic acid or diethylhydroxylamine, or derivatives or salts thereof, is especially preferred.
The presence of water in amounts of from about 60% to about 95% by weight of the solution system in the color developer concentrate enables easy mixing and solubility of all components within the color developer concentrate. Herein, the xe2x80x9csolution systemxe2x80x9d is defined as the total quantity of both water and organic solvents. Preferably, water is present in the color developer concentrate in an amount of at least about 70%, preferably at least about 75%, more preferably at least about 80% and most preferably at least about 90%, by weight of the solution system in the color developer concentrate.
The organic solvent has a composition as shown in Formula I below and is present in an amount of from about 5% to about 40% by weight of the solution system in the color developer concentrate. Preferably, the organic solvent of Formula I is present in an amount of about 30% or less, preferably 25% or less, more preferably 20% or less, and most preferably 10% or less of the solution system. Use of the organic solvent of Formula I in amounts of 40% or less by weight of the solution system in the color developer concentrate has several advantages. For example, it is known that the presence of organic solvents in the developer replenisher or working strength developer may result in undesirable photographic performance effects such as poor image quality on some photographic color silver halide emulsions. This effect is minimized as the amount of organic solvent is reduced. Further, use of lower amounts of organic solvent reduces chemical cost and reduces the total biochemical oxygen demand of the processing effluent.
The organic solvent of Formula (I) has the following composition: 
wherein X is selected from the group consisting of xe2x80x94OR1, H and methyl; R1 is selected from the group consisting of H, acyl, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R2 and R4 can be the same or different and are independently selected from the group consisting of H, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl and substituted or unsubstituted heteroaromatic; R3 is selected from the group consisting of H, alkoxyl of 1 to 2 carbons, alkyl of 1 to 2 carbons, aryl, arylalkoxyl, aryloxycarbonyl and substituted or unsubstituted alkoxycarbonyl; n is an integer from 1 to 12; and m is 0 or 1. The compound of Formula (1) has a molecular weight of about 1,000 or less, preferably less then about 500.
Compounds of Formula (I) enhance the solubility of p-phenylenediamine or a derivative or salt thereof in the color developer concentrate and demonstrate substantial miscibility with water as evidenced by forming a clear solution, free from turbidity and phase separation. This enables formation of a single-part, single-phase, liquid color developer concentrate according to the present invention.
Preferred examples of the compound of Formula (I) include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, tetraethylene glycol, propanediol, butanediol, diethylene glycol monoethyl ether, triethylene glycol monophenyl ether, and propylene glycol monomethyl ether. Most preferred compounds of Formula (I) are ethylene glycol, diethylene glycol and triethylene glycol. Other compounds of Formula (I) as known to practitioners in the art may also be used.
Optionally, two or more organic solvents of Formula (I), each independently selected from Formula (II) or (III) as set forth below, may be used in combination to form the developer concentrate. Formulas (II) and (III) are defined as follows: 
wherein R2, R3, R4, n and m are defined as for Formula (I); R1xe2x80x2 is acyl, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl, or substituted or unsubstituted heteroaromatic; R2xe2x80x2 and R4xe2x80x2 are the same or different and are independently selected from H, alkyl of 1 to 2 carbons, alkenyl of 2 to 4 carbons, aryl, and substituted or unsubstituted heteroaromatic; R3xe2x80x2 is H, alkoxyl of 1 to 2 carbons, alkyl of 1 to 2 carbons, aryl, arylalkoxyl, aryloxycarbonyl and substituted or unsubstituted alkoxycarbonyl; nxe2x80x2 is an integer of 1 to 12; and mxe2x80x2 is 0 or 1.
Other water-soluble or water-miscible additives capable of enhancing the solubility of p-phenylenediamine or derivatives or salts thereof that are compatible with photographic development may also be added to the color developer concentrate to aid in forming a homogenous liquid color developer concentrate. Photographic compatibility herein means providing acceptable sensitometric performance and avoiding dye diffusion, accelerated image fading, edge-penetration of developer into a paper base, and the like, wherein other unacceptable effects of incompatible additives are known to practitioners in the art. Additional water-soluble additives may be present in an amount of from about 0.4 to about 40 g/L of the color developer concentrate. Suitable additives include, but are not limited to, benzyl alcohol and p-toluene sulfonic acid or its salt. Other suitable additives are known to practitioners in the art.
The weight ratio of water: organic solvent of at least about 60:40 in the solution system of the color developer concentrate ensures the formation of a single-part, single-phase, liquid color developer concentrate that is aqueous, stable, and compact, wherein the color developer concentrate will have a minimal solvent effect on photographic performance, is produced with low chemical, shipping and packaging costs, and has minimal environmental impact compared to previously known color developer concentrates. Use of a weight ratio of less than about 60:40 of water: organic solvent in the solution system of the color developer concentrate makes it difficult to achieve complete dissolution of all ingredients in the developer composition and may cause undesired photographic effects.
Herein, xe2x80x9ca single-part, single-phase liquidxe2x80x9d is defined to mean a mixture of two or more ingredients to form a homogenous liquid without phase separation, i.e., without showing multiple liquid layers, solid precipitation, turbidity or haziness of the final liquid mixture. Thus, the single-part, single-phase, liquid color developer concentrate of the invention is meant to be substantially free of solid particles.
To produce a color developer concentrate with increased solubility and compactness, potassium salts are known in the art as exemplified in Papai, U.S. Pat. No. 5,891,609, and Darmon et al, U.S. Pat. Nos. 6,017,687, 6,077,651, and 6,228,567, incorporated herein by reference. As demonstrated in the examples of these patents, and as known to practitioners in the art, it is preferred to maintain potassium as the predominate cation in color developer concentrates.
However, the inventors herein have surprisingly discovered that in order to achieve a highly compact, single-part, single-phase, liquid color developer concentrate using a mixture of water and organic solvent as the solution system, the ratio of [Na+]/[K+] must be significantly increased in order to enhance the salt solubility. In particular, the molar ratio of [Na+]/[K+] is desirably at least about 1:2 or greater, more preferably in a range of from about 1:1 to about 3:2, and most preferably at least about 2:1 or greater. The sodium and potassium ions are those supplied by a mixture of sodium and potassium salts that are present in the color developer concentrate.
Thus, the color developer concentrate preferably comprises dissolved alkaline components and inorganic and organic alkaline, in particular sodium salts, such as, but not limited to, NaOH and Na2CO3, in an amount such that the molar ratio of total [Na+]/[K+] in the developer concentrate composition is at least about 1:2 or greater, more preferably in a range of from about 1:1 to 3:2, and most preferably at least about 2:1 or greater.
The amount of the alkaline components is adjusted as known to practitioners in the art to provide a color developer concentrate having a pH range of from about 11 to about 13. The developer replenisher formed by diluting the color developer concentrate in water at a volume factor of about 2 to about 17 has a pH of about 10.0 to about 12.5, preferably 10.5 to 12.5. The working strength developer formed by diluting the color developer concentrate in water at a volume factor of about 2 to about 17 has a pH of about 9.0 to about 10.5.
Other developer components as known to practitioners in the art also may be added to the color developer concentrate. For example, one or more buffering agents may be present in the color developer concentrate in order to maintain the pH of the developer replenisher and working strength developer at desirable levels upon dilution of the color developer concentrate. Suitable buffering agents include, but are not limited to, inorganic alkali metal hydroxides, alkali metal carbonates, and the like. Alkali metal hydroxides desirably include lithium, sodium and potassium hydroxide. Alkali metal carbonates desirably include lithium, sodium and potassium carbonates. Other suitable buffering agents are known to practitioners in the art. The buffering agent may be present in the developer replenisher in an amount of from about 0.1 to 0.3 M of developer replenisher, preferably in an amount of from about 0.15 to 0.2 M of developer replenisher, though other suitable amounts outside these ranges may also be used, as known to practitioners in the art.
Other inorganic or organic antioxidants besides hydroxylamine or derivatives or salts thereof can be added to the color developer concentrate as preservatives to protect the color developing agent. The term xe2x80x9corganic preservativexe2x80x9d as used herein encompasses all organic compounds which when added to processing solutions for color photographic photosensitive materials function to inhibit degradation of p-phenylenediamine or derivatives or salts thereof. Specifically, a preservative as used herein prevents oxidation of p-phenylenediamine or a derivative or salt thereof by air (aerial oxidation). Especially effective organic preservatives include, but are not limited to, hydroxamic acids, hydrazines, hydrazides, phenols, (alpha)-hydroxyketones, (alpha)-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitrosyl radicals, alcohols, oximes, diamides and fused ring type amines. These preservatives are disclosed in U.S. Pat. Nos. 2,494,903; 3,615,503; 4,155,764; 4,801,521; and 5,063,142. Other useful preservatives are known to practitioners in the art and may include, but are not limited to, metals as disclosed in U.S. Pat. No. 4,330,616; salicylic acids as disclosed in JP-A 180588/1984; amines as disclosed in U.S. Pat. Nos. 4,798,783 and 5,250,396; polyethylene imines as disclosed in U.S. Pat. No. 4,252,892; and aromatic polyhydroxy compounds as disclosed in U.S. Pat. No. 3,746,544. All patents referred to are incorporated herein in their entirety by reference.
Inorganic preservatives as known to practitioners in the art may be added to the working strength developer and developer replenisher in addition to one or more organic preservatives as described herein. The inorganic preservatives may be present in an amount from about 0.4 to about 8 mM of the developer replenisher, preferably in an amount of from about 0.8 to about 2 mM of the developer replenisher.
The single-part, single-phase, liquid color developer concentrate of the present invention may further contain other developer components known to practitioners in the art such as, but not limited to, various chelating agents as precipitation inhibitors of calcium or magnesium, or as stability improving agents of the developer. Examples thereof include, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,Nxe2x80x2,Nxe2x80x2-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,Nxe2x80x2-bis(2-hydroxybenzyl)ethylenediamine-N,Nxe2x80x2-diacetic acid and 1,2-dihydroxybenzene-4,6-disulfonic acid. These chelating agents may be used in combinations of two or more, if desired. The amount of chelating agent present in the color developer concentrate should be sufficient to sequester Group II and transition metal ions in the dilution water used to prepare the developer replenisher or working strength developer. For example, the color developer concentrate may contain chelating agents in an amount of from about 0.1 to about 10 g/L of the color developer concentrate, depending on the hardness of the dilution water. Lesser or greater amounts may also be appropriate, as determinable by practitioners in the art.
One or more optical brightening agents as known to practitioners in the art can also be added to the color developer concentrate, if necessary, in an amount of from about 0.1 to about 10 g/L, preferably from about 0.3 to about 5 g/L, of the color developer concentrate, although lesser or greater amounts may also be used as appropriate, as determinable by practitioners in the art. Preferred brighteners include 4,4xe2x80x2-diamino-2,2xe2x80x2-disulfostilbene compounds, although other suitable brighteners will be apparent to practitioners in the art. Compounds of the following general Formula (V) are especially preferred in the developer composition: 
wherein X and Y may be the same or different, and are selected from the following: 
Brightening agents that can be used in combination with a compound of Formula (V) may be selected from commercially available diaminostilbene brighteners. Such commercially available diaminostilbene compounds are described, for example, in Dyeing Note, 19th Ed., Senshoku-sha, pp. 165-168; T. Ruble, Optical Brighteners, Noyes Data Corp., (1972); and Handbook Textilhilfsmittel, (1977) pp. 645-66, which are incorporated herein by reference. Other suitable brightening agents are known to practitioners in the art.
Other additives such as antifoggants, alkanolamines, development accelerators, development restrainers, wetting agents, fragrances and surfactants, for example, as would be readily known to practitioners in the art, can optionally be included in the color developer concentrate. A detailed description of various color developer concentrate compositions and methods of processing such compositions is given, for example, in Research Disclosure 38 957 of September 1996, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, Great Britain, and Modern Photographic Processing, by Grant Haist, John Wiley and Sons, 1973, Volumes 1 and 2, herein incorporated by reference. Amounts of each additive suitable for use in the color developer concentrate of the invention are readily determinable by practitioners in the art.
Conventional packages or containers as known to practitioners in the art, for example, polyethylene and other plastic bottles, may be used for packaging the single-part, single-phase, liquid color developer concentrate after preparation thereof. Suitable packages and containers and methods of packaging the color developer concentrate in such packages and containers are known to practitioners in the art.
The color developer concentrate of the invention is used after dilution in water by a volume factor of about 2 to about 17 to form a working strength developer or a developer replenisher. The developer replenisher is normally continually added to the working strength developer tank in the photographic processor to maintain developer effectiveness as the working strength developer becomes exhausted with continued use, evaporates, becomes contaminated with emulsion extractives during processing or is oxidized, such as by oxygen in the air. The usable range of replenishment rate is from about 40 ml/m2 to about 110 ml/m2 of processed silver halide photosensitive material, depending on various factors as described above and known to practitioners in the art. More preferably, the replenishment rate is from about 45 mil/m2 to about 75 ml/m2 of processed silver halide photosensitive material using the color developer concentrate of the invention as described herein.
After diluting the color developer concentrate in water by a volume factor of about 2 to about 17, the diluted color developer concentrate provides a working strength developer with a pH range of about 9.0 to about 10.5, or a developer replenisher with a pH range of about 10.0 to about 13.0, preferably from about 10.5 to about 12.5.
Another feature of the invention is to provide a method for processing an image-wise exposed photographic color silver halide emulsion. The method includes mixing the color developer concentrate with water to form a working strength developer, and processing the exposed photosensitive material with the working strength developer. While optional processing parameters are known to practitioners in the art, preferably the process is carried out for about 20-90 seconds at a temperature of from about 30-45xc2x0 C.
Use of the above process with the color developer concentrate of the invention for developing image-wise exposed photographic color silver halide emulsions avoids the possibility of mixing errors inherent in using conventional sets of multiple liquid concentrates which must be mixed in a specific addition order prior to use. In the process of the invention, the color developer concentrate may be added manually to the developer replenisher tank containing dilution water by pouring at prescribed intervals, or it can be metered into the developer replenisher tank containing dilution water based on the actual quantity of photographic material processed, or based on some measured property of the process bath such as, for example, the specific gravity or pH of the working tank solution, the concentration of depleted components therein as determined by chemical analysis, the accumulation of decomposition products, the accumulation of extracts from the photographic material, other properties known to practitioners in the art, or any combination of the foregoing.
As compared with prior art single-part liquid concentrate compositions, the invention is characterized by ease in pouring, ease of mixing with water and the elimination of viscous or gummy matter that is difficult to solubilize and/or may adhere to photographic material. These attributes ensure good quality in the photographic materials processed. Further, as compared with the prior art, the single-part, single-phase, liquid color developer concentrate according to the present invention is simple to manufacture, requiring no in-process filtration or precipitate washing procedure. Further, by the use of organic solvents in an amount of less than or equal to about 40% by weight of the solution system in the color developer concentrate, the potential effect of organic solvent on the sensitometric character of various color photographic papers is minimized, chemical costs are lowered, and the environmental impact is lessened.
Additionally, with respect to the preparation of the processing solution using the color developer concentrate of the invention, handling is simplified and productivity is high because the possibility of mixing error is substantially reduced. As compared with a ready-to-use solution, the color developer concentrate of the invention has significantly reduced volume and weight, contributing to savings in transportation cost and storage space. Because there is only one container, the amount of packaging material is reduced, providing advantages of economy, lower recycling burden and enhancing environmental protection.